CN116297901A - Application of triazine-bithiophene covalent organic framework in enrichment and detection of nitrofuran metabolites in meat products - Google Patents
Application of triazine-bithiophene covalent organic framework in enrichment and detection of nitrofuran metabolites in meat products Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 19
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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Abstract
The invention belongs to the technical field of analytical chemistry and food safety detection, and discloses application of a triazine-bithiophene covalent organic framework in enrichment and detection of nitrofuran metabolites in meat products. The invention adopts the covalent organic framework compound solid phase extraction adsorbent, simplifies the sample extraction process, establishes a new method for sensitively analyzing nitrofuran metabolites in meat products based on the solid phase extraction and liquid-mass combination technology, and can better separate target substances from coexisting matrixes, so that the method has higher standard adding recovery rate and lower detection limit.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry and food safety detection, and particularly relates to application of a triazine-bithiophene covalent organic framework in enrichment and detection of nitrofuran metabolites in meat products.
Background
Nitrofurans are broad-spectrum antibiotics, have a killing effect on various pathogens, and are widely applied to livestock and poultry and aquaculture industries to prevent and treat various diseases. Due to the advantages of broad antibacterial spectrum, good effect, low cost, convenient use and the like of the nitrofurans, the nitrofurans are still used in the industries of livestock and poultry and aquaculture even if the national law prohibits. However, these drugs have great toxic and side effects, which can cause cell mutagenesis, resulting in irreversible myocardial toxicity, reproductive dysfunction and potential carcinogenesis, teratogenicity and mutagenicity. Nitrofurans have been currently classified by the national department of agriculture as forbidden drugs, prohibiting detection in animal foods. Nitrofurans are rapidly metabolized in animals and are difficult to detect, but metabolites of nitrofurans can be combined with proteins in the bodies and stably exist for a long time, so that nitrofurans are generally taken as target analytes to detect the residual quantity of nitrofurans.
Because of the complex matrix, the livestock and poultry meat can be detected after a series of pretreatment steps such as extraction, purification and the like. Solid phase extraction is a mature environment-friendly technology commonly used for sample pretreatment at present, namely, the samples are extracted and then pass through SPE columns to remove the interferences such as fat, phospholipid and the like in the matrixes. The selective adsorption properties of the solid phase extraction adsorbent are key factors for the purification effect in this step. There are Oasis HLB, MCX and C on the market 18 The solid phase extraction adsorbents are various, but the adsorbents have the defects of high price, few adsorption types and the like, and the development of novel solid adsorbents is a non-two option for developing solid phase extraction technology.
The covalent organic framework material is a compound formed by connecting light elements such as C, N, O and the like through stronger covalent bonds, and attracts much attention of a plurality of researchers in recent years as a porous material. The compound has higher thermal stability, lower structural density and regular and ordered pore canal. The pore channel property and the pore diameter can be regulated by adjusting the structure of the monomer, and the porous material can be widely applied to the fields of gas storage, catalysis, chromatographic separation, chemical sensors and the like, and can also be used as an excellent solid-phase extraction adsorbent or an adsorption coating.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide application of a triazine-bithiophene covalent organic framework in enrichment and detection of nitrofuran metabolites in meat products. As a solid-phase extraction adsorbent, the method is used for purifying and enriching nitrofuran metabolites in meat products, and combines a liquid chromatography-mass spectrometry technology to establish a detection method for sensitively analyzing the nitrofuran metabolites
The aim of the invention is achieved by the following technical scheme:
an application of triazine-bithiophene covalent organic skeleton in enriching and detecting nitrofuran metabolites in meat products.
The triazine-bithiophene covalent organic framework is prepared by the following method: 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 2,2 '-bithiophene-5, 5' -dicarboxaldehyde are taken as raw materials, placed in 1, 4-dioxane, dropwise added with glacial acetic acid, synthesized at normal temperature under the catalysis of the glacial acetic acid, and the obtained product is washed, dried in vacuum and ground to obtain a triazine-bithiophene covalent organic framework (TAPT-BPDD COF).
The molar ratio of the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the 2,2 '-bithiophene-5, 5' -dicarboxaldehyde is 2:3; the volume ratio of the 1, 4-dioxane to the acetic acid is 3:1; the 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 1, 4-dioxane are used in a molar volume ratio of 1mmol:8-10mL; the washing is carried out by adopting tetrahydrofuran and methanol to wash sequentially.
The enrichment and detection of nitrofurans metabolites in meat products comprises the following steps: and (3) pretreating a meat product to be detected by adopting a triazine-bithiophene covalent organic framework to obtain a sample, and detecting the obtained sample by adopting an ultra-high performance liquid chromatography-four-rod time-of-flight mass spectrometry.
The pretreatment specifically comprises the following steps:
(1) Filling 40-60 mg of triazine-bithiophene covalent organic frameworks into SPE small columns; balancing the SPE small column with 1-3 mL of methanol and water respectively;
(2) Derivatizing meat food to be detected with 2-nitrobenzaldehyde at 35-37 ℃ under acidic condition for 15-17 h, adding dipotassium hydrogen phosphate as buffer solution, adjusting pH to 7.0-7.5 by sodium hydroxide, and extracting by ethyl acetate to obtain extract; the dosage of the ethyl acetate and the meat food to be detected is 1g according to the volume-mass ratio (3-5) mL;
(3) Concentrating and drying the extracting solution obtained in the step (2) through nitrogen blowing, dissolving and diluting with water, degreasing twice through n-hexane, centrifuging, and passing the lower extracting solution through the SPE small column well balanced in the step (1);
(4) Eluting the SPE small column by using eluent, wherein the eluent is an aqueous solution containing 5-10% of methanol by volume percent;
(5) Eluting the SPE small column by using methanol eluent containing acetic acid or acetonitrile eluent containing acetic acid, wherein the volume percentage of the acetic acid in the eluent is 5-10%; drying the eluent by nitrogen, and re-dissolving by using an initial mobile phase to obtain a sample.
The specific operation of the step (2) is as follows: adding 200-300 mu L of 2-nitrobenzaldehyde methanol solution with the concentration of 0.05mol/L and 8-10mL of hydrochloric acid solution with the concentration of 0.2mol/L into 2g of meat food to be detected, and derivatizing for 15-17 h in a water bath with the temperature of 35-37 ℃; returning to room temperature, adding 3-5 mL of K with the concentration of 0.2mol/L 2 HPO 4 The solution is used as buffer solution, and NaOH is used for adjusting the pH value to 7.0-7.5; then adding 6-10 mL of ethyl acetate, carrying out ultrasonic treatment for 10min, centrifuging to obtain supernatant, repeatedly adding ethyl acetate for extraction once, and combining the extracting solutions.
Parameters of the ultra performance liquid chromatography-quaternary rod time-of-flight mass spectrometry include: reversed phase chromatographic column C 18 Separating, namely performing gradient elution by taking an acetonitrile solution containing 0.1% formic acid and an aqueous solution containing 0.1% formic acid as mobile phases, adopting an electrospray ion source (ESI) to ionize, scanning by a primary mass spectrum in a positive ion mode, wherein the scanning range is m/z=50-650 Da, the scanning speed is 0.5spectra/s, and monitoring and analyzing by using a four-level rod time-of-flight mass spectrum; the temperature of the ion source is 120 ℃; the desolventizing gas temperature is 350 ℃; the flow rate of the desolventizing gas is 650L/h; the air flow rate of the taper hole is 50L/h; collision voltage 30VThe method comprises the steps of carrying out a first treatment on the surface of the The taper hole body voltage is 40V; capillary voltage 2500V.
The gradient elution procedure was: the mobile phase takes an aqueous solution containing 0.1% formic acid as phase A and an acetonitrile solution containing 0.1% formic acid as phase B, and the gradient elution procedure is as follows: 1-2min,10-20% B;2-5min,20-30% B;5-7min,30-100% B;7-9min,100% B;9.1-10min,10% B; the flow rate is 0.3mL/min, the sample injection amount is 2 mu L, and the chromatographic column temperature is 40 ℃.
Compared with the prior art, the invention has the following advantages and effects:
(1) The triazine-bithiophene covalent organic framework adopted by the invention has good thermal stability and chemical stability, has good selectivity in adsorbing organic molecules containing benzene rings or nitrogen heterocycles, has good specific adsorption effect on nitrofuran metabolites in meat products, high enrichment efficiency and good labeling recovery rate, and can be repeatedly used for more than 5 times.
(2) The pretreatment process for detecting the nitrofurans metabolite residues in the meat products is simplified, the operation is simple, the pretreatment workload is reduced, the use amount of organic solvents is reduced, and the toxic hazard is reduced.
(3) The detection method adopted by the invention has high sensitivity, can efficiently detect the content of nitrofurans metabolite residues in meat products, and has good reproducibility, low detection limit and high labeling recovery rate.
Drawings
FIG. 1 is an infrared spectrum of TAPT-BPDD COF and its monomers.
FIG. 2 is an XRD pattern for TAPT-BPDD COF.
FIG. 3 is a thermogram of TAPT-BPDD COF.
FIG. 4 is an SEM image of TAPT-BPDD COF.
FIG. 5 is a graph of the adsorption and desorption of nitrogen from TAPT-BPDD COF.
FIG. 6 is a pore size distribution diagram of TAPT-BPDD COF
FIG. 7 is a graph showing the results of solid phase extraction in example 2, wherein (a) is an optimized graph of the amount of adsorbent, (b) is an optimized graph of the pH of the sample, (c) is an optimized graph of the ratio of eluting solvents, (d) is an optimized graph of the types of eluting solvents, (e) is an optimized graph of the amount of eluting solvents, and (f) is a graph of the number of times of recycling of TAPT-BPDD COF.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention.
Example 1: preparation of solid phase extraction adsorbent based on TAPT-BPDD COF material
Adding 531.6mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 500.0mg of 2,2 '-bithiophene-5, 5' -dicarboxaldehyde into 15mL of 1, 4-dioxane, adding 5mL of glacial acetic acid after ultrasonic treatment for 20min, standing at normal temperature for 3 days, washing tetrahydrofuran and methanol for 3 times, drying at 120 ℃ in vacuum for 12 hours, and grinding to obtain red solid powder, namely triazine-bithiophene covalent organic framework (TAPT-BPDD COF material).
Characterization of the resulting TAPT-BPDD COF material:
the functional groups of the synthesized TAPT-BPDD COF material are confirmed by infrared spectroscopy (FT-IR). 3448cm in FIG. 1 -1 The strong peak at this point can be attributed to stretching vibration of the-NH-bond, 1654cm -1 The decrease in peak at this point indicates that aldehyde groups have been involved in the reaction; 1629cm -1 The peak at this point was attributable to the-C-N-C-stretching vibration of the imide, indicating that the amine group had reacted with the aldehyde group.
The crystallinity of the resulting TAPT-BPDD COF material was characterized by X-ray diffraction (XRD). From FIG. 2, TAPT-BPDD COF is an amorphous material.
The thermal stability of the resulting TAPT-BPDD COF material was characterized by thermal gravimetric curve (TGA). From fig. 3, the compound can be stabilized to 450 ℃.
The morphology of the resulting TAPT-BPDD COF material was characterized by Scanning Electron Microscopy (SEM). From fig. 4, the synthesized powder is a particle with a diameter of about several hundred nanometers.
The specific surface area of the TAPT-BPDD COF material is characterized by a nitrogen adsorption and desorption curve. From the analysis of FIG. 5, the synthesized material had a specific surface area of 14.3cm 3 /g。
The pore structure composition of the resulting TAPT-BPDD COF material was characterized by pore size distribution. From fig. 6, the synthesized material is a porous material containing micropores and mesopores.
Example 2: sample pretreatment and solid phase extraction process
2g of the homogenized meat sample was weighed into a 50mL centrifuge tube, 300. Mu.L of 2-nitrobenzaldehyde solution (0.05 mol/L, dissolved in methanol) and 10mL of hydrochloric acid solution (0.2 mol/L) were added, and after vortex mixing, the mixture was subjected to a light-resistant water bath at 37℃for 16 hours. After returning to room temperature, 5mL K was added 2 HPO 4 The solution (0.2 mol/L) is used as buffer solution, and NaOH is used for adjusting the pH value to 7.0-7.5; adding 10mL of ethyl acetate into the sample, carrying out ultrasonic treatment for 10min after vortex, centrifuging to obtain supernatant, repeatedly extracting once, combining the extracting solutions, concentrating the extracting solution to be nearly dry, adding 5mL of water for ultrasonic redissolution, and degreasing twice with 3mL of n-hexane; the upper liquid is discarded, and the lower liquid is passed through a solid phase extraction column.
Taking 40mg of TAPT-BPDD COF material obtained in the example 1 in a 3mL SPE small column, and respectively activating solid phase extraction filling materials in sequence by 3mL of methanol and 2mL of water; purifying the treated sample at a sample loading speed of 3mL/min, eluting with 2mL of an aqueous solution containing 5% by volume of methanol, discarding the eluent, eluting with 2mL of a methanol solution containing 5% by volume of glacial acetic acid, collecting the eluent, drying with nitrogen, re-dissolving with an initial mobile phase, filtering with a 0.22 mu m filter membrane, and loading for testing.
The extraction conditions are optimized and investigated in the experiment: with reference to the conditions in example 2, single-factor optimization experiments were performed, respectively.
Different amounts of adsorbent (20, 40, 60, 80 mg), different sample pH values (3, 5, 7, 9, 11), different methanol contents in the eluting solvent (0%, 5%, 10%,) different eluting solvents (methanol, ethanol, acetonitrile, ethyl acetate, methanol with 5% glacial acetic acid, methanol with 5% ammonia water), different eluent amounts (1 mL, 2mL, 3mL, 4 mL) were tested, as in fig. 7, the following optimum conditions were finally selected: the dosage of the adsorbent is 40mg, the pH value of the sample is not adjusted, the methanol content in the eluent is 5%, the eluting solvent is methanol containing 5% glacial acetic acid, and the dosage of the eluting solvent is 2mL.
Example 3: liquid chromatography-mass spectrometry detection flow of 4 nitrofurans metabolites
ACQUIT equipped with Waters Xevo G2 QTOFY
BEH C 18 And (3) detecting, namely taking water containing 0.1% of formic acid by volume percentage as a phase A, and acetonitrile containing 0.1% of formic acid by volume percentage as a phase B, wherein the gradient elution procedure is as follows: 1-2min,10-20% B;2-5min,20-30% B;5-7min,30-100% B;7-9min,100% B;9.1-10min,10% B; 2. Mu.L of sample was introduced and the column temperature was 40 ℃. Ionization by electrospray ion source, primary mass spectrum scanning under positive ion mode, scanning range of m/z=50-650 Da, and four-level rod time-of-flight mass spectrum monitoring analysis. The temperature of the ion source is 120 ℃; the desolventizing gas temperature is 350 ℃; the flow rate of the desolventizing gas is 650L/h; the air flow rate of the taper hole is 50L/h; a collision voltage of 30V; the taper hole body voltage is 40V; capillary voltage 2500V. Primary mass spectrum ion [ M+H ] of four nitrofuran metabolites] + The retention times are shown in table 1.
The method is established and applied to evaluate:
under the optimal condition, the detection limit, the quantitative limit, the linear range and the precision of the method are examined, the correlation coefficient is between 0.992 and 0.996, the detection limit is between 0.05 and 0.56 mug/kg, and the details are shown in Table 2.
To verify the practicality of the established method, the method was applied to the detection of nitrofurans metabolites in 3 total actual samples of fish, chicken and pork. Accurately weighing 2g of homogeneous blank sample, adding a proper amount of nitrofurans metabolite mixed standard working solution with different concentrations to prepare three addition levels of 5 mug/kg, 20 mug/kg and 50 mug/kg, processing the sample according to the sample pretreatment method and the solid phase extraction flow of the embodiment 2, and calculating the recovery rate and precision of each concentration addition level by using a standard curve linear equation, wherein the result is shown in Table 3, and the addition recovery rate is 72.7% -111.6%.
Table 1 Primary Mass Spectrometry ion of analytes [ M+H ]] + Retention time
Table 2 method detection limits, quantitative limits, linear ranges and precision
Table 3 labelling recovery and precision of nitrofurans metabolites in food samples
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. An application of triazine-bithiophene covalent organic skeleton in enriching and detecting nitrofuran metabolites in meat products.
2. The use according to claim 1, characterized in that: the triazine-bithiophene covalent organic framework is prepared by the following method: 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 2,2 '-bithiophene-5, 5' -dicarboxaldehyde are taken as raw materials, placed in 1, 4-dioxane, dropwise added with glacial acetic acid, synthesized at normal temperature under the catalysis of glacial acetic acid, and the obtained product is washed, dried in vacuum and ground to obtain the triazine-bithiophene covalent organic framework.
3. The use according to claim 2, characterized in that: the molar ratio of the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the 2,2 '-bithiophene-5, 5' -dicarboxaldehyde is 2:3; the volume ratio of the 1, 4-dioxane to the acetic acid is 3:1; the 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and 1, 4-dioxane are used in a molar volume ratio of 1mmol:8-10mL; the washing is carried out by adopting tetrahydrofuran and methanol to wash sequentially.
4. The use according to claim 1, characterized in that: the enrichment and detection of nitrofurans metabolites in meat products comprises the following steps: and (3) pretreating a meat product to be detected by adopting a triazine-bithiophene covalent organic framework to obtain a sample, and detecting the obtained sample by adopting an ultra-high performance liquid chromatography-four-rod time-of-flight mass spectrometry.
5. The use according to claim 4, characterized in that: the pretreatment specifically comprises the following steps:
(1) Filling 40-60 mg of triazine-bithiophene covalent organic frameworks into SPE small columns; balancing the SPE small column with 1-3 mL of methanol and water respectively;
(2) Derivatizing meat food to be detected with 2-nitrobenzaldehyde at 35-37 ℃ under acidic condition for 15-17 h, adding dipotassium hydrogen phosphate as buffer solution, adjusting pH to 7.0-7.5 by sodium hydroxide, and extracting by ethyl acetate to obtain extract; the dosage of the ethyl acetate and the meat food to be detected is 1g according to the volume-mass ratio (3-5) mL;
(3) Concentrating and drying the extracting solution obtained in the step (2) through nitrogen blowing, dissolving and diluting with water, degreasing twice through n-hexane, centrifuging, and passing the lower extracting solution through the SPE small column well balanced in the step (1);
(4) Eluting the SPE small column by using eluent, wherein the eluent is an aqueous solution containing 5-10% of methanol by volume percent;
(5) Eluting the SPE small column by using methanol eluent containing acetic acid or acetonitrile eluent containing acetic acid, wherein the volume percentage of the acetic acid in the eluent is 5-10%; drying the eluent by nitrogen, and re-dissolving by using an initial mobile phase to obtain a sample.
6. The use according to claim 5, characterized in that: the specific operation of the step (2) is as follows: adding 200-300 mu L of 2-nitrobenzaldehyde methanol solution with the concentration of 0.05mol/L and 8-10mL of hydrochloric acid solution with the concentration of 0.2mol/L into 2g of meat food to be detected, and derivatizing for 15-17 h in a water bath with the temperature of 35-37 ℃; recoveryAfter the temperature reaches the room temperature, 3 to 5mL of K with the concentration of 0.2mol/L is added 2 HPO 4 The solution is used as buffer solution, and NaOH is used for adjusting the pH value to 7.0-7.5; then adding 6-10 mL of ethyl acetate, carrying out ultrasonic treatment for 10min, centrifuging to obtain supernatant, repeatedly adding ethyl acetate for extraction once, and combining the extracting solutions.
7. The use according to claim 4, characterized in that: parameters of the ultra performance liquid chromatography-quaternary rod time-of-flight mass spectrometry include: reversed phase chromatographic column C 18 Separating, namely performing gradient elution by taking an acetonitrile solution containing 0.1% formic acid and an aqueous solution containing 0.1% formic acid as mobile phases, adopting an electrospray ion source to ionize, scanning by a primary mass spectrum in a positive ion mode, wherein the scanning range is m/z=50-650 Da, the scanning rate is 0.5spectra/s, and performing monitoring analysis by using a four-level rod flight time mass spectrum; the temperature of the ion source is 120 ℃; the desolventizing gas temperature is 350 ℃; the flow rate of the desolventizing gas is 650L/h; the air flow rate of the taper hole is 50L/h; a collision voltage of 30V; the taper hole body voltage is 40V; capillary voltage 2500V.
8. The use according to claim 7, characterized in that: the gradient elution procedure was: the mobile phase takes an aqueous solution containing 0.1% formic acid as phase A and an acetonitrile solution containing 0.1% formic acid as phase B, and the gradient elution procedure is as follows: 1-2min,10-20% B;2-5min,20-30% B;5-7min,30-100% B;7-9min,100% B;9.1-10min,10% B; the flow rate is 0.3mL/min, the sample injection amount is 2 mu L, and the chromatographic column temperature is 40 ℃.
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